Polyphosphate compositions containing soap and 2-mercaptothiazoline



United States Patent 2,861,954 I POLYPHOSPHATE COMPOSITIONS CONTAININGSOAP AND Z-MERCAPT'DTHIAZOLINE Edgar E. Ruff, Bergeniield, N. .L,assignor to Lever Brothers Company, New YorlqN. Y., a corporation ofMaine No Drawing. Application January 9, 1956 Serial No. 557,854 13Claims. (Cl. 252-110) This invenion relates to detergent compositionscontaining tarnish inhibitors and more particularly to spraydriedtripolyphosphate compositions containing a soap and Z-mercaptothiazolineas synergistic tarnish inhibitors.

Tripolyphosphate compositions are now widely used for detergent andother purposes. Aqueous solutions of such compositions when at certainpH values tend to tarnish German silver (a nickel-Zinc-copper alloy) toa variety of shades from yellow to bluish black, especially if thesolutions are at elevated temperatures and are allowed to remain incontact with the metal for several minutes. Since German silver isfrequently used for household articles commonly washed intripolyphosphatebuilt detergent compositions, it is evident that this isa serious problem.

In developing a spray-dried tripolyphosphate detergent compositioncontaining an organic anionic non-soap detergent or an organic nonionicnon-soap detergent it was found that Z-mercaptothiazoline was aneffective tarnish inhibitor for such compositions. However, it was alsofound that when such spray-dried tripolyphosphate compositions containfrom about 10% to about 20% of an alkali metal carbonate thatZ-mercaptothiazoline no longer was effective as a tarnish inhibitor.This is clearly shown by the six examples presented below in Table Iwherein the amounts of the components in the tripolyphosphate detergentcompositions are expressed in percent by weight of the total compositionat the time of mixing the components together with the exception of theZ-mercaptothiazoline tarnish inhibitor, the percent thereof being basedupon the weight of the tripolyphosphate present in the compositions. Inthefollowing six examples Pluronic L64 is an organic nonionic non-soapdetergent compound having the empirical formula HO(C H O) (C H O) (C HO) H prepared by condensing ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycolwhere b is an integer selected from the group consisting of 26 to 30 anda plus is an integer such that the molecule contains from 40% to 50% ofethylene oxide and Oronite Dispersant NIW is an organic nonionicnon-soap detergent which is a polypropylene alkyl phenol averagingtetradecyl in the alkyl radical condensed with ethylene oxide to anaverage of 9 ethylene oxide groups.

TABLE I Example No 1 2 3 4 5 6 Pluronic L-04 8. 75 8. 75 8.75 8. 75 8.75 8. 75 Oronite Dispersant NIW 1.25 1. 25 1. 25 1.25 1. 25 1. 25Pentasodium Tripclyphosphateun 35. 0O 35. 00 35. 00 35. 00 35. 00 35. 00Sodium Car-boxymethyl Hydroxyethyl Cellulose. 0. 50 0. 5O 0. 50 0. 50 0.50 0. 50 Water 10.00 10.00 10.00 10.00 10.00 10.00 Sodium Sulfate. 44.50 40. 75 37.00 33. 25 29. 50 24. 50 Sodium Carbonate. 0.00 3. 75 7. 5011.25 15.00 20.00

Total 100. 00 100. 00 100. 00 100. 00 100.00 100. 00

Z-Mereaptothiazoline (based on tripolyphosphate)... 0.06 0.06 0.06 0 060.06 0.06 Tarnish Grade No. l 2 3 5 5 5 The tarnishing action of each ofthe above tripolyphosphate detergent compositions on German silver wastested by the following procedure. Five grams of the tripolyphosphatedetergent composition was dissolved in somewhat less than one quart ofWater at a temperature under 17-0" F. More water was then added to givea total volume of one quart. 300 ml. of the solution was placed in abeaker, and the temperature adjusted to F.- F. A strip of German silvermetal, six inches by one inch which had been cleaned with a metal polishand rinsed and dried, was partially immersed in the solution and allowedto remain for one-half hour at 160 F.-170 F. The metal strip was thenremoved and dried with a cloth. The strip was visually examined fortarnish and the tarnish graded as follows.

Grade N 0. Degree of Tarnish No tarnish.

Interface stain only.

Barely noticeable tarnish.

Slight tarnish.

Moderate tarnish.

Considerable (heavy) tarnish. Severe, as when inhibitor is absent.

This test procedure was employed throughout the remaining examplesherein set forth.

From Example 1 above it can be readily seen that a tripolyphosphatedetergent composition containing at least one organic non-soap detergentand containing 2- mercaptothiazoline produces only interface stain uponGerman silver when the composition does not contain any alkali metalcarbonate. As the amount of alkali metal carbonate is increased and theamount of alkali metal sulfate supplemental builder correspondinglydecreased it canbe seen that the 2-mercaptothiazoline loses itseffectiveness as a tarnish inhibitor and becomes ineffective when thealkali metal carbonate content is in the range from about 10% to about20%. The compositions of Examples l--6 were prepared as mechanical mixesrather than as spray-dried products in order that the proportions ofsodium carbonate would not be altered by possible decomposition uponspray drying. It will be appreciated, however, that the results notedabove also apply to spray-dried products.

In accordance with the instant invention it wasfound that spray-driedtripolyphosphate detergent compositions containing at least one organicnon-soap detergent and from about 10% to about 20% of an alkali metalcarbonate could be provided with greatly improved tarnishing propertiesupon German silver when such compositions contain Z-mercaptothiazolineand soap as synergistic tarnish inhibitors. The spray-dried detergentcompositions of the present invention which will inhibit the formationof tarnish upon German silver therefore comprise by weight from about20% to about 50% of an alkali metal tripolyphosphate, fromabout 5% toabout 15% total of at least one organic non-soap detergent selected fromthe group consisting of organic anionic nonsoap detergents and organicnonionic non-soap detergents, from about 10% to about 20% of an alkalimetal carbonate, about 10% of an alkali metal silicate, from about 0.03%to about 0.06% of 2-mercaptothiazoline based on the weight oftripolyphosphate, from about 1.4% to about 3.0% of a soap based on theweight of tripol'yphosphate, said soap being selected from the groupconsisting of alkali metal salts of fatty acids having an acyl-group offrom 8 to 22 carbon atoms, and the balance water and supplementalbuilders. These components and percentages thereof are expressed at thetime of mixing the components together and prior to spray drying. p

Any water-solublealkali metal tripolyphosph ate may be employed,examples thereof being pentasodium tripolyphosphate and pentapotassiumtripolyphosphate. From about 20% to about 50%, and preferably about 35%,by weight of the alkali metal tripolyphosphate is present in thedetergent composition as the heavy duty component thereof. From about toabout 15% total, and preferably about total, by weight of at least oneorganic non-soap detergent is employed in the composition. organicanionic non-soap detergents or organic nonionic non-soap detergents. Itwas found that the synergistic tarnish inhibitors were ineffective withorganic cationic non-soap detergents and hence such detergents areexcluded from the detergent compositions.

The organic anionic non-soap detergents include by way of example thealkylaryl sulfonates, a class of anionic detergents well known in theart under this name. One example thereof is the sulfonated phenylpolypropylene alkanes, characterized by the branched chain structure ofpolypropylene and a tertiary alkyl carbon at the benzene ring, andhaving the following general structure:

where M is hydrogen, an alkali metal or an organic amine cation, and Rand R are alkyl, of the type formula C H and at least one R is apolypropylene group, the whole alkyl group containing preferably 12 to15 carbon atoms. These are known compounds, whose preparation andproperties are set forth in U. S. Patent No. 2,477,383 to Lewis, issuedJuly 26, 1949; they are available in commerce under the trade namesOronite, Ultrawet, and Neolene.

N-onionic detergents include, for example, alkyl oxyether and ester andthioether and ester detergents having the following general formula:

where R is a straight or branched chain saturated or unsaturatedhydrocarbon group having from 8 to 18 carbon atoms or an aralkyl grouphaving a straight or branched chain saturated or unsaturated hydrocarbongroup of from 8 to 18 carbon atoms attached to the aryl nucleus, andattached to A through the aryl nucleus, A is selected from the groupconsisting of ethereal oxygen and sulfur, carboxylic ester andthiocarboxylic ester groups and x is a number from 8 to 20. R can, forexample, be a straight or branched chain octyl, nonyl, decyl, lauryl,myristyl, cetyl or stearyl group, or an alkylaryl group such asoctylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc.

When R is alkyl it will be evident that the detergent can be regarded asderived from an alcohol, mercaptan, oxy or thio fatty acid of highmolecular weight, by condensation with ethylene oxide. Typical of thisclass of alkyl ether are the condensation products of oleyl or dodecylalcohol or mercaptan with from 8 to 17 moles of ethylene oxide, such asEmulfor On, Nonic 2l8.and Sterox SE and SK. Typical alkyl esters areG1226 Renex (polyoxyethylene ester of tall oil acids), Sterox CD andNeutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).

When R is aralkyl, the detergent can an alkyl phenol or thiophenol. V

The ethoxynated alkyl phenols and thiophenols have the following generalformula:

be derived from where R is a straight or branched chain saturated orunsaturated hydrocarbon group having at least 8 carbon The organicnon-soap detergents may be either 4 atoms up to approximately 18 carbonatoms, A is oxygen of sulfur and x is a number from 8 to 20. R can, forexample, be a straight or branched chain octyl, nonyl, decyl, lauryl,cetyl, myristyl or stearyl group. Typical V, are the condensationproducts of octyl and nonyl phenol and thiophenol with from 8 to 17moles of ethylene oxide,

available commercially under the trade names NIW, Antarox A-400, IgepalCA and CO, Triton X-100,Neutronyx 600, and Tergitol NFX.

The alkali metal carbonate may be by way of example sodium carbonate orpotassium carbonate, from about 10% to about 20%, and preferably 15% byweight thereof being employed in the detergent composition.

The alkali metal silicate may be sodium or potassium silicate, forexample, the amount thereof being about 10%.

As noted above one of the synergistic tarnish inhibitors is2-mercaptothiazoline. From about 0.03% to about 0.06% thereof based onthe weight of tripolyphosphate is employed in the spray-dried detergentcomposition.

The other synergistic tarnish inhibitor is a soap, from about 1.4% toabout 3.0% thereof based on the weight of tripolyphosphate beingemployed in the detergent composition. The soap is an alkali metal saltof one or more of the higher saturated or unsaturated fatty acids havingan acyl group of from 8 to 22 carbon atoms and may include, for example,the alkali metal salts, such as the sodium salts of myristic acid,palmitic acid, tallow fatty acid, and coconut oil fatty acid.

The balance of the spray-dried detergent composition is made up of waterand supplemental builders. The supplemental builders may include alkalimetal and alkaline'earth metal sulfates, chlorides, and borates, such assodium tetraborate, sodium sulfate, calcium sulfate, calcium chloride,sodium chloride, and sodium borate. The builders should bewater-soluble.

In addition to or instead of the above mentioned supplemental inorganicsalts, organic material, such as starch, polyethylene glycols, polyvinylalcohols and salts of carboxymethylcellulose and carboxymethylhydroxyethyl.

cellulose and perfumes and dyes can be used in minor proportions asbuilders.

The tripolyphosphate detergent compositions may be prepared by theconventional method of blending the ingredients thereof in an aqueoussolution or slurry and then drying the resulting mixture in a spraydryer at elevated temperatures. -It was found that with drumdriedtripolyphosphate detergent compositions that the synergistic tarnishinhibitors were not necessary in order to prevent the formation oftarnish by such compositions upon German silver. Accordingly, drum-driedtripolyphosphate detergent compositions are excluded from thisinvention.

The invention will be further explained by the following discussion.Drum-dried tripolyphosphate detergent compositions do not need thepresence of the synergistic tarnish inhibitors, since the components ofsuch compositions do not decompose upon drum drying. Accordingly, the10% of alkali metal silicate added to the mixture of the compositionprior to drum drying remains present inthe same amount in the drum-driedproduct and is sufiicient by itself in this amount to inhibit theformation of tarnish upon German silver by the tripolyphosphate. This,however, is not true of spray-dried tripolyphosphate detergentcompositions.

In the conventional spray drying of tripolyphosphate detergentcompositions there is a decomposition of a portion of the alkali metaltripolyphosphate into such products as alkali metal pyrophosphate. Forexample, a mixture of the tripolyphosphate detergent composition inExample 9 without the synergistic tarnish inhibitors upon spray dryingcontained about 10% of tetrasodium pyrophosphate as determined by wetanalysis. There is also a decomposition of a portion of the alkali metalsilicate into silica floc by the acidic breakdown products of the alkalimetal tripolyphosphate, thereby reducingthe silicate content to about68%. Accordingly, there is an insulficient amount of silicate present inthe spray-dried product to inhibit the formation of tarnish Moreover,the presence of pyrophosphate in the spray-dried product resulting fromthe decomposition of tripolyphosphate in creases the tarnishing effectof the spray-dried product, since alkali metal silicate is much lesselfective as a tarnish inhibitor against pyrophosphates than againsttripolyphosphates.

The of alkali metal silicate would be efiective as a tarnish inhibitorin tripolyphosphate detergent compositions containing from 10% to 20% ofalkali metal carbonate if there were no decomposition of thetripolyphosphate and silicate upon spray drying. Since there is suchdecomposition, it is necessary in accordance with the invention toemploy the synergistic tarnish inhibitors therein.

The compositions of the invention will be further illustrated inconnection with the following examples. Spraydried tripolyphosphatedetergent compositions were prepared having the following percentagecompositions by weight, at the time of mixing the components togetherand prior to spray drying. In Examples 9 and 10 the fluorescent dye wasthe disodium salt of 4,4-bis| [4-phenylamino 6 [bis(2 hydroxyethyl)lamino s triazine 2- ylaminol|-2,2' stilbene disulfonic acid.

Example 7 PART A Percent Sodium dodecylbenzene sulfonate 10 Pentasodiumtripolyphosphate 35 Sodium silicate 10 Sodium carbonate Sodiumcarboxymethyl hydroxyethyl cellulose 0.5 Water 10 Sodium sulfate 19.48 2mercaptothiazoline 1 0.02

Total 100 2-mercaptothiazo1ine (based on tripolyphosphate) 0.06%.

PART B Percent Sodium dodecylbenzene sulfonate 10 Pentasodiumtripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodiumcarboxymethyl hydroxyethyl cel1ulose 0.5 Water 10 Sodium sulfate 18.48 2mercaptothiazoline 1 0.02 Sodium tallow soap 2 1.00

Total 100 Z-mercaptothiazoline (based on tripolyphosphate) 0.06%.

2 Sodium tallow soap (based on tripolyphosphate) 2.9%.

Example 8 PART A q Percent Sodium hardened-tallow alcohol sulfate c 10Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Sodium sulfate19.48 Z-mercaptothiazoline 1 0.02

Total 100 2-mercaptothiazoline (based on tripolyphosphate) 0.06%.

6 PART B Percent Sodium hardened-tallow alcohol sulfate 10 Pentasodiumtripolypho-sphate 35 Sodium silicate 10 Sodium carbonate 15 Sodiumcarhoxymethyl hydroxyethyl cellulose 0.5 Water 10 Sodium sulfate 18.48Z-mercaptothiazoline 1 0.02 Sodium tallow soap 2 1.00

Total 2=mercaptothiazoline (based on tripolyphosphate) 0.06%. Sod1umtallow soap (based on tripolyplhosphate) 2.9%.

Example 9 PART A Percent Pluronic L-64 8.75 Oronite dispersant NIW 1.25Pentasodium tripolypho-sphate 35 Sodium silicate 10 Sodium carbonate 15Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye0.03 Sodium sulfate 19.47

Total 100 Z-mercaptothiazoline (based on tripolyphosphate) 0.03

PART B Percent Pluronic L-64 8.75 Oronite dispersant NIW 1.25Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15Sodium carboxymethyl hydro-Xyethyl cellulose 0.5 Water 10 Fluorescentdye 0.03 Sodium sulfate 19.47

Total 100 Z-mercaptothiazoline (based on tripolyphosphate) 0.03 Sodiumtallow soap (based on tripolyphosphate) 1.4

Example 10 PART A Percent Pluronic L64 8.75 Oronite dispersant NIW 1.2 5Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye0.03 Sodium sulfate 19.47

Total .a... 100

2-mercaptothiazoline (based on tripolyphosphate) 0.06

7 8 R B tages thereof. Accordingly, it will be understood that Percentthe invention is to be limited only within the scope of the PluronlcL-64 8.75 a d d l ppen e calms. Oronlte dlspersant NIW 1.25 I claim:zggzi i gig ig 1. A spray-dried detergent composition consisting es-Sodium carbOnat-e 15 sentlallypf from about 20% to about 50% of analkali Sodium carbox ggz zg g g O 5 metal trlpolyphosphate which 1naqueous solution tar- Water y y y 3 y mshes German s1lver, from about 5%to about total g ug 0 03 of at least one organic non-soap detergentselected from S 19'47 10 the group consistmg of organic anionic non-soapdeter- 0 mm Su ac gents and organic nonionic non-soap detergents, fromabout 10% to about of an alkali metal carbonate, Total 100 about 10% ofan alkali metal silicate, from about 0.03% zmercaptothiazofine (based onm 01 he to about 006% of Z-mercaptothiazoline based on the h t p yp S 15weight of tripolyphosphate, and from about 1.4% to S 3. 6) f '1 006about 3.0% of a water-soluble alkali metal soap based 0 i ta ow Soap(based on mpolyphos' on the weight of tripolyphosphate, said soap beingsep a e) lected from the group consisting of the alkali metal salts Theconditions set forth in Table II below were emof fatty acids having anacyl group of from 8 to 22 carployed in the spray-drying of thecompositions in Exambon atoms; the amounts of said thiazoline and soapbeing P sufficient to inhibit the tarnishing and the components of TABLEII Example No 7A 7B 8A 13 0A 9B 10A 10B Percent Water in Slurry 29 29 3333 35 35 20 20 Slurry Temperature F). 185 185 185 185 160 160 185 185Total Mixing Time (minutes) 30 30 30 30 30 Mixing Time After PhosphateAd ion (minutes) 10 10 10 10 l0 10 Tower Air Inlet Temperature F.) 540540 540 540 400-450 400450 500-600 520 Examples 9A and 9B were preparedby adding 2-merthe composition being expressed by weight at the timecaptothiazoline (and soap) in solution to a solution of of mixingthereof and prior to spray drying. the product, which was spray-driedwithout Z-mercapto- 2. A spray-dried detergent composition as set forththiazoline or other synergist. These examples differ in in claim 1wherein the amount of alkali metal tripolythis respect fromthe otherswhich were spray-dried after phosphate is about 3 addition ofZ-mercaptothiazoline (and soap) to the 3. A spray-dried detergentcomposition as set forth crutcher slurry. in claim 1 wherein the alkalimetal tripolyphosphate is The tarnishing action of each of thespray-dried deterpen a di m rip yp p gent compositions in Examples 7-10upon German silver 4. A spray-dried detergent composition as set forthwas tested in accordance with the above described test in Claim 1containing about 10% total of at least one procedure. The followingresults were noted. Organic p detergent- 5.'A spray-dried detergentcomposition as set forth in claim 1 wherein the organic non-soapdetergent is so- Example 5351 Degree ofTamjsh dium dodecylbenzenesulfonate.

6. A spray-dried detergent composltlon as set forth in claim 1 whereinthe organic non-soap detergents are a 3 Slight tar shmixture of (l) acompound having the empirical formula 2 ittfittttttsil 2 )acsnfi nwzm wP p by 2 Barely noticeable tarnish. 5O densing ethylene oxide with ahydrophobic base formed liarrushby the condensation of propylene oxidewith propylene 5 Considerable (heavy) tarnish. glycol where b is aninteger selected from the group con- 1 Interface Siam sisting of 26 to30 and a plus c is an integer such that the molecule contains from 40%to of ethylene The compositions in part A of each of Examples 7 10oxide, and polypropylene alkyl p o averaging contained an alkali metaltripolyphosphate, at least one totfadeoyl in the alkyl Tadloal CondonsodWlth ethylene organic anionic or nonionic non-soap detergent, an alkaliOXide to an average of 9 ethylene OXld? p metal carbonate, an alkalimetal silicate, supplemental A p ydetergent composltlon as sot forthbuilders and one of the synergistic tarnish inhibitors, in'olaim 1containing about 15% of an alkali metal namely Z-mercaptothiazoline. Inthese compositions 2- bollatomercaptothiazoline alone was ineffective asa tarnish in- A p ydetergent composition as set forth hibitor, since thecompositions tarnished German silver in Claim 1 wherein the alkali metalcarbonate is Sodium to a degree of tarnish ranging from slight tarnishto con- Carbonatesiderable tarnish. The compositions in part B of eachof A p ydetergent composition as Set forth Examples 7 -10 were as notedabove with the exception in claim 1 wherein the Water-soluble alkalimetal soap is that an alkali metal soap was also added thereto so-thatSodium tallOW P- each of these compositions contained the synergistictar- A p ydotofgont Composition Consisting nish inhibitors, namely,2-mrcaptothiazoline and an alsentially of from about 20% to about 50% ofpentasokali metal soap. The compositions in part B showed a diumtripolyphosphate Which in aqueous solution tarvery noticeableimprovement over the corresponding comnishes German silver, from about5% to about 15% of positions in part A, thereby demonstrating the remarksodium dodecylbenzene sulfonate, from about 10% to able effectiveness ofthe synergistic tarnish inhibitors. about 20% of sodium carbonate, about10% of sodium Various modifications and changes may be made in thesilicate, from about 0.03% to about 0.06% of Z-mercapcompositions ofthis invention Without departing from tothiazoline based on the weightof tripolyphosphate, and the spirit of the invention or sacrificing anyof the advanfrom about 1.4% to about 3.0% of sodium tallow soap K is.

9 based on the weight of tripolyphosphate; the amounts of saidthiazoline and soap being sutficient to inhibit the tarnishing and thecomponents of the composition being expressed by Weight at the time ofmixing thereof and prior to spray drying.

11. A spray-dried detergent composition consisting essentially of about35% of pentasodium tripolyphosphate which in aqueous solution tarnishesGerman silver, about 10% of sodium dodecylbenzene sulfonate, about 15%of sodium carbonate, about 10% of sodium silicate, from about 0.03% toabout 0.06% of Z-mercaptothiazoline based on the Weight oftripolyphosphate, and from about 1.4% to about 3.0% of sodium tallowsoap based on the Weight of tripolyphosphate; the amounts of saidthiazoline and soap being sufiicient to inhibit the tarnishing and thecomponents of the composition being expressed by Weight at the time ofmixing thereof and prior to spray drying.

12. A spray-dried detergent composition consisting essentially of fromabout 20% to about 50% of pentasodium tripolyphosphate which in aqueoussolution tarnishes German silver; from about to about 15% total of amixture of (1) a compound having the empirical formula HO(C H O) (C H-O) (C H O) H prepared by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propylene glycolwhere b is an integer selected from the group consisting of 26 to 30 anda plus c is an integer such that the molecule contains from 40% to 50%of ethylene oxide, and (2) a polypropylene alkyl phenol averagingtetradecyl in the alkyl radical condensed with ethylene oxide to anaverage of 9 ethylene oxide groups; from about 10% to about 20% ofsodium carbonate; about 10% of sodium silicate; from about 0.03% toabout 0.06% of 2-mercaptothiazoline based on the weight oftripolyphosphate; and from about 1.4% to about 3.0% of sodium tallowsoap based on the weight of tripolyphosphate; the amounts of saidthiazoline and soap being suflicient to inhibit the tarnishing and thecomponents of the composition being expressed by Weight at the time ofmixing thereof and prior to spray drying.

13. A spray-dried detergent composition consisting essentially of about35% of pentasodium tripolyphosphate which in aqueous solution tarnishesGerman silver; about 10% total of a mixture of (1) a compound having theempirical formula HO(C H O) (C H O);,(C H O) H prepared by condensingethylene oxide with a hydrophobic base formed by the condensation ofpropylene oxide With propylene glycol Where b is an integer selectedfrom the group consisting of 26 to 30 and a plus c is an integer suchthat the molecule contains from to of ethylene oxide, and (2) apolypropylene alkyl phenol averaging tetradecyl in the alkyl radicalcondensed with ethylene oxide to an average of 9 ethylene oxide groups;about 15% of sodium carbonate; about 10% sodium sill cate; from about0.03% to about 0.06% of Z-mercaptothiazoline based on the Weight oftripolyphosphate; and from about 1.4% to about 3.0% of sodium tallowsoap based on the weight of tripolyphosphate; the amounts of saidthiazoline and soap being sufiicient to inhibit the tarnishing and thecomponents of the composition being expressed by weight at the time ofmixing thereof and prior to spray drying.

References Cited in the tile of this patent UNITED STATES PATENTS2,486,922 Strain Nov. 1, 1949 2,618,603 Schaeffer Nov. 18, 19522,622,068 Hizer Dec. 16, 1952 FOREIGN PATENTS 156,852 Australia June 3,1954 157,971 Australia Aug. 2, 1954

1. A SPRAY-DRIED DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROMABOUT 20% TO ABOUT 50% OF AN ALKALI METAL TRIPOLYPHOSPHATE WHICH INAQUEOUS SOLUTION TARNISHES GERMAN SILVER, FROM ABOUT 5% TO ABOUT 15%TOTAL OF AT LEAST ONE ORGANIC NON-SOAP DETERGENT SELECTED FROM THE GROUPCONSISTING OF ORGANIC ANIONIC NON-SOAP DETERGENTS AND ORGANIC NONIONICNON-SOAP DETERGENTS, FROM ABOUT 10% TO ABOUT 20% OF AN ALKALI METALCARBONATE, ABOUT 10% TO AN ALKALI METAL SILICATE, FROM ABOUT 0.03% TOABOUT 0.06% OF 2-MERCAPTOTHIAZOLINE BASED ON THE WEIGHT OFTRIPOLYPHOSPHATE, AND FROM ABOUT 1.4% TO ABOUT 3.0% OF A WATER-SOLUBLEALKALI METAL SOAP BASED ON THE WEIGHT OF TRIPOLYPHOSPHATE, SAID SOAPBEING SELECTED FROM ACIDS HAVING AN ACYL GROUP OF FROM 8 TO 22 CAROFFATTY ACIDS HAVING AN ACYL GROUP OF FROM 8 TO 22 CARBON ATOMS; THEAMOUNTS OF SAID THIAZOLINE AND SOAP BEING SUFFICIENT TO INHINIT THETARNISHING AND THE COMPONENTS OF THE COMPOSITION BEING EXPRESSED BYWEIGHT AT THE TIME OF MIXING THEROF AND PRIOR TO SPRAY DRYING.